加拿大玩具安全标准 Method C-03 2009版

Part B: Test Methods Section, Method C03

Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),

and Barium (Ba) in Applied Coatings. 70

1Scope

1.1This method describes a general procedure for the determination of leachable

arsenic, selenium, cadmium, antimony, and barium in decorative or protective

coatings applicable to item 9(c) of Part I, Schedule I of the Hazardous Products

Act ( SOR 2005-344 ).

2Applicable Documents

2.1Standard Practice for Use of the Terms Precision and Bias in ASTM Test

Methods. Volume 14.02, ASTM E177-90a (1996), pp.79-90.

2.2Standard Practice for Intra laboratory quality Control Procedures and a

Discussion on Reporting Low-Level Data. Volume 11.01, ASTM D4210-89,

pp.412-419, 1998.

2.3John Keenan Taylor, Quality Assurance of Chemical Measurements. Lewis

Publishers, INC. 328 pages, 1987.

2.4National Standard of Canada - Methods of test for toxic trace elements in

protective coatings. CGSB Standard Test Method 1-GP-500.2, 1-GP-500.3, 1-

GP-500.4, 1-GP-500.5, 1-GP-500.7. Specifications Board. (December, 1973).

CGSB Standard Test Method 1-GP-500.2 (December, 1973).

2.5 C. Watson, “Update of Method C-03, Determination of Leachable Cadmium (Cd),

Barium (Ba), Antimony (Sb), Selenium (Se) and Arsenic (As) in Applied

Coatings.” Product Safety Laboratory, Project Report No. 2004-0801. (Nov.

2004)

2.6 A. Babcock, “Update of Method C-03, Determination of Leachable Arsenic (As),

Selenium (Se), Cadmium (Cd), Antimony (Sb), and Barium (Ba) in Applied

Coatings.” Product Safety Laboratory, Project Report No. 2005-0881. (Oct.

2007)

Part B: Test Methods Section, Method C03

Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),

and Barium (Ba) in Applied Coatings. 70

3Reagents and Apparatus(Note 1)

3.1ICP-MS Agilent 7500a equipped with an internal standards addition Tee

3.2Arsenic, Selenium, Cadmium, Antimony and Barium standards, 1000 ppm, or

As, Se, Cd, Sb, Ba (+ others) multi-element standard 10.0 ppm ± 0.5%, SCP

Science or equivalent, traceable to NIST, for calibration

3.310.0 ppb As, Se, Cd, Sb, Ba calibration control standard

3.4Gallium, Indium and Bismuth standards, 1000 ppm (nominal), SCP Science or

equivalent, traceable to NIST, for internal standards

3.5Ultra-pure (18.2 M S) water, free of As, Se, Cd, Sb, Ba

3.6Hydrochloric acid, concentrated (- 37% w/w), Trace Metal Grade, Fisher

Scientific

3.7Nitric acid, concentrated (- 69% w/w), Trace Metal Grade, Fisher Scientific

3.8Scalpel or other suitable scraping tool.

3.9Tetrahydrofuran (THF) HPLC Grade, Caledon Laboratories, Ltd.

3.10Electric grinder

3.11Mortar and pestle

3.12Air convection oven

3.13Desiccator

3.14Sieves, 250 and 500 :m mesh

3.15Sample bottles for sieved paint

3.16Analytical Balance, with a precision of 0.1mg

3.17Weighing vessels

3.18Glass beakers, 50 mL

3.19Oscillating hot plate or magnetic stirrer

3.20Filter paper, Whatman no. 40

3.21Funnels to fit 50 mL flasks or tubes

3.22Volumetric flasks, 50 mL, 2 L

3.23Sample tubes, screw cap, 50 mL certified volume

3.24Pipettes adjustable 10 - 100 :L, 100 - 1000:L, 0.500 - 2.50 mL, 1.00 - 10.00 mL

3.25NIST SRM 1633b, Coal Fly Ash, used as a control

Note 1:Equivalent materials and apparatus may be used.

Part B: Test Methods Section, Method C03

Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),

and Barium (Ba) in Applied Coatings. 70

4Experimental Procedure

4.1Scrape off the applied coating from the test sample with a scalpel, or other

suitable scraping tool, being careful not to remove any of the underlying

substrate material. Alternatively, the coating can be removed with

tetrahydrofuran (THF) or a suitable solvent (Note 2), and collected into an

appropriate vessel. Evaporate the solvent from the removed coating and dry to

constant weight (to the nearest 1 mg) in an air convection oven at 60°C ± 3°C.

This may take several hours. Remove the vessel from the oven and cool in a

desiccator.

4.2Transfer the removed coating to a mortar and grind the sample with a pestle. An

electric grinder may be used when the sample is too difficult to grind with a pestle

and a mortar. Sieve the ground coating with a 500 :m sieve. The sample

passing through the 500 :m sieve is then sieved through a 250 :m sieve. The

portion of the ground coating that passes the 500 :m and does not pass the 250

:m is used for the leaching test. Place the sieved portion in a weighing vessel

and dry to constant weight (to the nearest 1 mg) in an air convection oven at

60°C ± 3°C. This may take about an hour. Remove the vessel from the oven

and cool in a desiccator.

4.3Prepare the 5% (v/v) HCl leaching solution by diluting 50 mL of concentrated

(approx. 37% w/w) hydrochloric acid to 1000mL with ultra-pure water.

4.4Transfer about 100 mg of the dried coating into a tared 100 mL beaker and weigh

to the nearest 0.1 mg. Add 20 mL of the 5% (v/v) HCl leaching solution and

immediately start stirring for 10 ± 1 minutes at 20°C ±3°C with the use of an

oscillating hotplate or a magnetic stirrer. At the end of the 10 ± 1 minutes,

immediately filter the solution, through a Whatman no. 40 filter paper in a funnel,

into a 50 mL volumetric flask or certified 50 mL sample tube, wash with a few mL

of ultra-pure water, add 1 mL of concentrated nitric acid, and make up to volume

with ultra-pure water. At least three replicate analyses should be performed on

each coating sample.

4.5Prepare a blank solution by adding 20 mL of the 5% (v/v) HCl leaching solution to

a 100 mL beaker and immediately start stirring for 10 ± 1 min. at 20oC ± 3oC with

the use of an oscillating hotplate or a magnetic stirrer. At the end of the 10 ± 1

min. immediately filter the solution, through a Whatman no. 40 filter paper

Note 2:Acetone or dichloromethane may be used to facilitate the removal of the applied coating, solvents like tetrahydrofuran should not be used if the test article's substrate material is a plastic.

Part B: Test Methods Section, Method C03Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),

and Barium (Ba) in Applied Coatings. 70 and a funnel, into a 50 mL volumetric flask or certified 50 mL sample tube, wash with a few mL of ultra-pure water, add 1 mL of concentrated nitric acid, and make up to volume with ultra-pure

water.

4.6Prepare a 2.0% (v/v) nitric acid diluting solution by diluting 20 mL of concentrated (approx. 69% w/w) nitric acid to 1000mL with ultra-pure water.4.7Dilute the worked-up leachate ten times using 2% (v/v) nitric acid (the 50 mL

leachate from section 4.4).

5Calibration

5.1Prepare an acid solution consisting of 0.2% (v/v) hydrochloric acid and 2.0% (v/v)nitric acid in a 2 L volumetric flask. Use 4 mL of conc. HCl and 40 mL of conc.HNO 3 and make up to 2 L volume with ultra-pure water. This solution will be

used as a blank solution, to prepare calibration standard solutions, and to dilute samples that are over the linear dynamic range of the instrument.5.2Prepare a series of at least three working calibration standards in the linear

range of the detector of the instrument to obtain a linear calibration curve with a

correlation coefficient of at least 0.99. These standards should be in the following range: 0 ppb to 100 or 200 ppb diluted from a 10 ppm solution of the five elements. Make up all calibration standards in 0.2% (v/v) hydrochloric acid

and 2.0% (v/v) nitric acid.5.3Prepare about 100 - 250 mL of a 100 ppb solution of the internal standards Ga,

In, Ba in 5% nitric acid. This solution is pumped into the internal standard

addition Tee (on the back of the peristaltic pump) where it mixes with the sample

before going to the spray chamber of the ICP-MS.

5.4Prepare separately from the standards a 10 ppb multi-element calibration control

solution, or buy it ready-made with a NIST traceable certificate of analysis.

5.5Analyse the calibration standards using a minimum of five replicate readings in

the ICP-MS method. Use the same ICP-MS method that will be used for the

blanks, controls, and samples. Obtain a calibration curve of ion counts per

second vs. concentration and check it for suitability (e.g. outliers & linearity /

curve fitting) for each element before proceeding with the analysis of the

samples.

Part B: Test Methods Section, Method C03

Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),

and Barium (Ba) in Applied Coatings. 70

6Determination

6.1Analyse the method blank before and after each batch of samples.

6.2Check the calibration by analysing the 10 ppb multi-element calibration control

solution. If the calibration is not in control, it may be necessary to re-make the

control solution and / or the calibration standards.

6.3Analyse the control sample (NIST 1633b - coal fly ash) for all five elements.

Record the results in the logbook method control chart (Use CCPro software).

6.4Analyse the sample solutions using a minimum of five replicate readings in the

ICP-MS method. The use of nine or more replicate readings gives better

statistics, but results in slightly longer analysis times. If necessary, dilute the

sample with 0.2% HCl and 2.0% HNO 3 (as prepared in § 5.1) to keep the results

within the range of the calibration.

7Calculations and Reporting

7.1Calculate the percentage by weight of leachable elements in the dry coating test

sample according to the following equation:

Leachable elements % (w/w) = Ci × 50 × 10 × Df

m × 10,000,000

where:

Ci =Concentration of element in the leaching solution (ppb) from the

instrument § 6.4

50 =Volume of worked-up leachate (filtered, rinsed, acidified) § 4.5

10 =Dilution of leachate § 4.7

Df =Further Dilution factor (if required to stay within calibration) § 6.4

m =mass (g) of test sample used § 4.4

10,000,000 =ppb / percent

7.2Where the quantity of sample for testing is sufficient and where practicable, the

result of analysis shall be reported as the average of a minimum of three

independent replicate determinations having a precision which should not differ

more than the specifications defined in section 8.

Part B: Test Methods Section, Method C03

Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb), and Barium (Ba) in Applied Coatings. 70Note 3:The standard deviation (s) of the test results may be calculated according to the following equation,

where x i is the result of an individual determination, 0 is the average of the replicate determinations,and n is the total number of replicates.

__________

s = ' (x i ! 0)2 .

r (n !1)

7.3Where applicable, the average (x.x × 10 +e ) and the sample standard deviation (s.s × 10 e ) of replicate determinations (s for n > 2) shall be calculated (Note 3),

and the result of analysis reported in the following format:Sample No.

Specimen No.Colour /Description [As]Leachable % (w/w)[Se]Leachable % (w/w)[Cd]Leachable % (w/w)[Sb]Leachable % (w/w)[Ba]Leachable % (w/w)S-1001234

1A red paint (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e S-10012342A blue paint (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e

8Quality Control Procedure

8.1To ensure the proper operation of the instrument and that the precision of the

analytical measurements meet the specifications of the method, the following

quality control procedures shall be conducted concurrently with the analysis of

the test sample.

8.2

The normal and correct operation of the ICP-MS shall be verified according to the

following guidelines:

8.2.1Run the ICP-MS Tune program and verify that the values (ion counts per

second) for the tuning solution elements (typically Li Y Tl) are within

acceptable limits of the historical values. A slow decline in the numbers is

to be expected as the detector wears out over a period of about two

years. Record the tuning element values in the ICP-MS logbook and

include a copy of the tune program printout in the sample or report file. If

the tuning values are too low, re-tune the instrument to get acceptable

values. Minimum acceptable values are Li 6400, Y 16000, Tl 9600 .

Part B: Test Methods Section, Method C03

Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),

and Barium (Ba) in Applied Coatings. 70

8.3The normal and correct operation of the test method shall be verified according

to the following guidelines:

8.3.1Conduct an analysis of the leachate of NIST SRM 1633b, coal fly ash,

tested under identical experimental conditions (except for grinding and

sieving) to those of the coating sample. Record the analytical test results

for all of the elements in the ICP-MS QC logbook. Verify that the results

are within acceptable limits on the control chart, and if so, enter a note in

the sample folder(s) to the effect that the test method was found to be

"within control". If the test results of the control sample fall outside the

specifications of the method, the entire analytical procedure shall be

repeated.

9Precision and Bias

9.1Repeatability (r): The deviation between replicate test results, as obtained from

analysis of NIST 1633b (coal fly ash) by the same analyst using the same

instrument under constant operating conditions, in the normal and correct

operation of the test method, should not differ by more than the following

repeatability limit at a 95% probability level (1.960 × %2 × CV% = 2.772 × CV%).

As: 11%Se: 100%Cd: n/a Sb: n/a Ba: 50%

9.2Bias: The bias cannot be established due to the absence of an accepted

“leachable” reference value in paint.

10Limit of Detection

10.1The limit of detection (LOD) of this method, as determined by ICP-MS has been

calculated (Note 4) to be:

Arsenic: 0.00018% (w/w)

Selenium: 0.00015% (w/w)

Cadmium: 0.00019% (w/w)

Antimony: 0.00043% (w/w)

Barium: 0.00041% (w/w)

Note 4: ASTM test method D4210.

Part B: Test Methods Section, Method C03

Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),

and Barium (Ba) in Applied Coatings. 70

11Limit of Quantitation

10.1The limit of quantitation (LOQ) of this method, as determined by ICP-MS has

been calculated (Note 5) to be :

Arsenic: 0.00055% (w/w)

Selenium: 0.00047% (w/w)

Cadmium: 0.00059% (w/w)

Antimony: 0.0013% (w/w)

Barium: 0.0012% (w/w)

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . End . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Note 5: ASTM test method D4210

Part B: Test Methods Section, Method C03

Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),

and Barium (Ba) in Applied Coatings. 70 L:\QualityAssurance\Quality\BOOK5\ENGLISH\Amendment 70\C03 Effective 2009-06-15.wpd